Derivatives of substituted aminonaphthalene substances.



NMANN RICHARI) Koran, Osmni I and Am'on Ossnxnnomdoctors. ofplulosoderrhein; Vohwinkehneer ElberfeldyMiil "UNITED "s1Ares, P T NTOFFICE.

nnmrwn mwmx, or; wmsnonr mnmnzmm; 'mcmum KOT'HE, or, vouwm'm, mumBLB'EBFELD; 08min nnEssEL; or. MfiLHEIM-ON-THERHINE, AND Ammo ossmumex,or COLOGNE, GERMANY, ASSIGNORS TO SYNTHETIC PATENTS 00., me, 01 NEWYORK, 1?. Y., A. conromu'xox or REwYonm i DEmi'ATIYEs or sUBs'rr'rU'rEnKMINbNAY HTHALENE suB s TANcEs.

To aZlwhpmit-hmyconc'efn: V

le'iitr known that we; BnnnmmogHnr- Dnnsssp,

phy, chemists, citizens of the German E pire,lresiding at; respectively,Wies dorf N ieheim on the Rhine,' and CoIogne-on-th'e- Rhine,.Gerniu'ny, have invented new anduse f u1 Improvements in DerivativesofSubstituted Arninonaphthalene Substances, of which the followlng is uspecification.

.j 'The-p1escnt inveritibhrelates to the pro- 'gluctionzof derivativesofija'minonaphthalene substances substitut'ed'in the'a'mino gr up bymeans of nitro derivatives of the 11:1 idsof :Ghcts and finallyeondensation of these sub '-20-=- stan ces-to ureids. The term ureids ishere used to include-the thioufeids as well asth'e ureid itself. r l

These substitution derivziti es of aminosnaphtholem'a substances may bea 25- ain substituted bythe above acid halids l The ureid s of thesesubstitutedHi mino v in which Astands for the radical of a nephthalcuecompound whichmay contain substituting groups, such. as hydroxyl OH,-.group, etc.,' R

halo en Cl, Br, I, the sulfo stun s. for the residue of an acid groupsuch as -CO- theresidue of the carhoxyl group; S( the residue of thesnlfonic" 'group, etc; and- Yifor an aromatic radical, such as phen-G,,H,, and t eir derivatives stanoes are substituted by such nitro ,derivatiye's offl halide paro-nitro-benzoylchlorid, metamitro-benfore myformlllar are reduced and condensed to furnish-the i or by ha ranitro-phenyl-urea ehloritl of the v 1 The reduction naphthalenesubstances 1s'carr1e(l'-out by 'means "of mm and acetic acid stitutedjamindnuplithalene substances are lene '-C;- na-phthylene .ureidsjwiththe'follmring or when treated with bisulfid of 'cerbon tofurnishthidureids with the following j formula; I 7

p fl i m-rmnr. Piite'nted Mai-(13,1917.

, Apbllcatlon mean" :9, i914." mm. 940,195. I

' Ass tinting .ma terial the aminohaphthm lene substances may beeulployedin the'form 45, of theinmonm, iii-, or higher sulfonatd derirativesin jthe form oi other derl'vati'ves or in the form of theaminonh'phthol 'de-j riviitiv'es. These uniinonephthalene" submeta-nitro-anisoyl-chlorid, etc.,-or by nitrolhenz'olsulfonyl-ehlorid ofthe for-mule ea or by 1 :5 -nitro-nz phthoylchlori d .of the formula V Tr-u!-c'o-c|.

- I. of these substituted umlnoy y other appropriate method;furnishuigproductsof the following general formula:

X1t:N P ;;L Finally these amino derivatives of the 'suh-=: 5

treated Withplmsgen, etc to furnish A 5 generalv If, as above storethencid-halids are repeutedlyinlrodm-ml into the umlnonuphlhalcue substances, derivatives of the fol lowing general form'ula are obtained:

which upon treatment with phosgen furnish ure'ids of the followinggeneral formuht:

In the same manner 'thrce,' four, or still moremolecules of the acidhallds nnght he int oduced into the uminolmplithalene nonaphthulenesubstances nitro derivatives of various ucid hulids. may be employed, sothat in the general iormulalast given one R may stand for ,CO andtheother for -SO,-, if nitro-lienzoyl chlorid and nitrobcnzol-sulfo-chloridwere used for introduction into the uminonu plithalcne substance. Thene\ v. products possess therapeutic are dissolved in about 000 parts ofwater and carbonate -of soda to .form the neutral salt. Then 50. partsof ealcined carbonate of sodium are added, and phosgen is introducedinto this solution at 40-410 L'in a. slow current until an aeidulatedtest poro tion" does not react any more with sodiumnitrate. The newacid' is salted out. By dissolving in carbonate of soda andsaltingare-dissolved in 'water 'and 'cui-honate of soda to form the neutralsalt. Then 50 aminonaphthaleneAli-ilisulfonic subsequent reduction whichpossesses the and with'bisulfid or carbon, thioureids of-the followingformula? value, as they show strong blood-parasite destroying qualitiesand comparatively small injurious eil'cut towar'd 'thehost.

Many of them are ulso'useful in the syn- 'thesis of azo dyestufl's usthey combine with diuzotized amms.

In carrying, out our process practically we may lFtroceedfas follows,the parts being by weig I Example 1: 56.5 parts of the acid sodium saltobtained 'by the action of para-nitrd benzoyl ,cl'llorid uponlulminonnphthalene- 8.6-di'sulfonic acid, subsequent reduction andintroduction oi the meta-nitro-benzoyl resi due into the resulting 'acidand subsequent reduction cipit'ate.

lExample 2: 62.5 parts of the acid sodium on t chloriil on the reducedsubstituted derivative obtained from nitrmmisoylcl\lorid and 1- ucidand.

it out again, it is obtained as a.white'prefollowing formula:

' parts of calcined sodiumcarbonate are added and phosgen 1H lntrmhu'edas in Example-L obtained by the action of nitroanisoylv 1 21a 05a z' ngreaetionis finished, if on additionlof Thefnew aeid mi tia-limo is themew, d jnitrite of sodium to an acidulatedt'est pot-l i-rigfotmula;

,\ Foiil lti diaz otat'ion takes place amyl more. 1, 1

Bydibsolving the acid in cnbonate of soda. nmindisulfonic acid or1.4.6.8-napht hylaminand galting 1110!; a ai'n, it 'i aa obtained as a'tliSlllfOl llC acid are employed. white incipitate. H [win veiry/ dilutesolu'v Example 3: 46 partsnf the acidsodiumq tions 0 will acid maketryplenosomes (lisape salt'of the substitution derivatiye obtained iOlpeaif from the blood of animalsinfedted with from the reaction ofJmru-nitnol enz0ylchl0- Q4 them. rid on'1.8-aminonaphtholkfi-(hslllfonic acid a In a like mennenureas'ofthiour eils with and subeqnent reduction which has the fob similar properties are obtained ifother s'ul lo wing' constitution:

ionic acids shah as' 2.5.71ior-2.3. 6-nnphth1fl are dissolved in 1000parts of water and action with nitrite which'means that there" treatedwith, carbonate ofsod1,funtil the is no amino substance jn'esent any.more; n'e'utfnl salt is formed. Then 50 pm'tsmf Alreadyklurin'g theoperation the ureidsep-N (-l-ystnllized sodium :lcctuteihre added/and.mites ,for the greatest part. Aftm the and \vl'lilmstirring phosgen isintroduced in :1 of. the reaction chlorifl '01: sodium iskuldcd 3b slowcurrent at a temperature of 40-45 in ofder to complete. the separation.The The treatment with phosgen is continued ffree'aeid hasthe'followingconstitutionj: r '10 until an acidulated test'ample shows noref l Y By dissolving the acid by-means of can sesstronglyltrypimosomesedestroying acllOl'lijlO of soda and sdhsequentaddition oi tion. -ll1e"aci l,' when coupled with-din.

, 10 chlm-id or'fmtlimIl; the neuit ml salt of the itizednnilimjlirnishes a clea-mhlne'me ye above acid iep'recipitatedasyellowi'sh'powstuff. (let. Dilute solutions of this gubstanee'po&

The neutral sodium salt of this acid after 15' coupled with diazotizedanilin.

add tion f 1 part Example 4: 60* parts of the neutral Sodium nahtlnol-Qfi-disulfonic acid and subsequent salt obtained by the doubleintroduction of recliictlon which possesses the following for- '5 themetanitrobenzoyl residue into 1.8-aminomul a A swirled with a refluxcondenser. The alcohol is distiliedofi and the acid is precipitated Ithas the following formulaf I are dissolved in about 700 parts of water,7 00 pe rts of alcohol are added and'after the of sulfur and 35 parts ofis boiled in a. vessel prot d i ii. co I CSyfthe mixture 7' Example 5:50 parts of the acid Sodium bein filtered anddried is a powder which issolugle in water with a yellowish color.

zols'u'lfonfylchlorid' on LS-aminonapththoh The acid also forms nodyestufis, \vhen 3.6-disu] onic acid and subsequent reduction whichposseses the following formula on Nil-B i and the required sodiumacetate soda to furnish the 50 parts of crystallized son are added anuphosgen s introduced as described in Example 1. T he thus formed acidhas the following formula:

are dissolved with water quantity of carbonate of neutral salt. Then onNib-e0 By dissolving the same with the addition of carbonate of soda.and precipitating it by rhlorid of sodium the neutral-salt is obtainedwhich is easily soluble in water. In the dry form the neutral salt is afaintly reddish zene. I

Examp le ti: 64.5 p-; k'ts'of the acid sodium salt obtained by-theaction of nitroa'nisoyl ohlorid on thereduced substituted derivasaltobtained by the action of meta-nitroben- 20f powder It forms azo dyeswith diazobem 36 possess strongliy sFirocharte-destroyin and enilin,

The treatment with lly dissolving the acid by means of 0511'- bonatc ofsoda and subsequent addition of chlorid of sodium, the neutral salt ofthe above acid' is precipitated as yellowish powder. Dilute. solutionsof this substance action. '-The aci ln coupled with himfurnishes a clearred dyestulf.

are dissolved in 1000 partsof water and treated with carbonate of soda,until the neutral s'altis formed. Then 50 parts of crystallized nodiumcarbonate are'added and whi-leetirring phosgen is introduced in a slowcurrent at a temperature of 4045 (3'. phosgen is continued until ana'cidulated test sampleshows no B dissolring the a id' by means. ofmbonate'of'eoda and Subsequent addition of abovaci'df; is precipitated ns' yellowish powder. Thej'ecId', when coupled with diamtizedunilinxfurnbhesi a clear red dyestufi'.

In a li I are iiisisolved about 1000 pertsio f water and-carbonate ofsoda to form the neutral salt. Then parts calcined sodium carnaphthol-4.(l-disul 1e 8: 63 parts vof the ncid'sodium e substitutionderivative obtained by condensation of para nitrochuuimylchlorid withthe product of the reaction of para-nitl'o-cinnamg'lchlorid on1.8aminoonic acil aucl subsequent reduction which has the followingconstitution:

Exam salt of t reaction with nitrite which means that, there is no ammomlbstauce present any more.

Already during g tbe operation the ureid separates for 'thegreatestpart. After the our] of the reaction chlorul of sodium is added in orderto complete the separation. The free acid has the followingconstitution:

aminonaphthol slilfonic'ec'id, 2.5.1.7, 145.52. 7- or 2.8.8.6a11pinonaphthplfdisulfonic acid are employed;

- Examwple 9, z"-l8;parts of the acid sodiunr .sa'lt obtainedbyt'he'fldulrle introduction of;

the metanit-robe -izoyl I' 9Sldll6f illt0 1-amino-8-ehloro-naphthalenfefifi-disulfonic acid and subsequent reduction whichpo sse'sseslthe following formula:

bonate ale addei'jamfl phosgen i g mauve-e1 into this soluti0nat40-50?Olin a; slow current until no diaeotation tukeis place any izja ibliedif o1 additiqg of nitrite of sodium no .dmzqta-tlol takee place anymore.The

.5 'By dissolfing the acid in carbonate of Soda. and salting it outagain, it is obtained as' a yenwish preqipitaite. .n a like' manner:ureas with similar pro gl ties ai'q jobcgined if other su'lfonicjici 10sud acijdiire'bmplbyed; or if inlstead of thenninoacidyl groups of.thegexamnles other acidyl ridicule a'i "ilitroduced, such '35 amix'io'phenyl-aceti-acid-hlorid. The same or different gcidyl radicals .oramirionaphthaleng' 'uhdiicau be used. -'A thou 11' we have abovedescribed exam,-

by igv' ich the ur'eids and thioureids my "jinde'rstoqd as therebyexcluding pquivalgms foi-th ingredintq-or the operations .g'gpployed inthe 'prqcss. It is probible that silbst qituu s, I fin, example,va'ribus kinds 'of 3mindhaiphthaine-Sfilfo acids, various halids ofamn'flitic acids nd of aromaticvsillfo m di- A mp by p r tii ofeinvetifiofilintenaed I fhtby."

1; As fiefi' 'pmduew' iil eids of ,BIibShtljMaminonaphth'alene'wubshnoes char'actenzed by conta ningjn iihaifuoiecule thege'nei al gmup, n a" ,numbep 1888 than 7, Xffor mil)- .inwhich R new acid thu formula:

4. 'Ai: new th w lds P w n mi WW? s 'aminonaphtho P flficts ureids ofsubstituted nmnanqihthol substances characterized b containing in theirmolecule the general group:

outlining in their, molecule the general l on i, c v -CD-QHc-NIL- A- fc" un-a-may-unw i i 9-8) 1 (80 H) -I m which :1 stands for a number lessthan 7 i in which R stands fortheresidueof an acid 1 up n a number lessthan five, and KT V w substituting groups"; forming salts with metals,and forming-azo.dyestuifs with diamtized anilin, substantially asdescribed.

7. As new product v ureids of substituted aminonaphthol substancescharacterized by containing in their molecule an aggregation of thegeneral groupi a i one ahmspmqmguu 90,11), in,whichR stands for adivalent group. con' taining an acidyl radical,,n'1 .a number less ithan 5, and Xfiior substituting/groups; formin salts with metals, andform ng azo dyestu s with diazotized auiliu, substmu tially asdescribed. S

8. As new products urcids of substituted aminonuphthol substancescharacterized by. containing in their molecule the 'general formula: t

Song) I e in which stands for theresidue of an acid ;group, formingsalts with metals, and form m z o dyestufi's with diazotized anilin,substantiallyias described. 3

aminonaphthol substances characterized? by .tuted aininonaphtholsubstances characterized by containing in tlieirmoleculefnn aggregatioiiof *thegeneralgroup? 1 H0) mI s -co-c.nt iml t s "in which n standstoriu numberless than seven, X for substituting roupsjfofmm salts withmetals,-nndform1ng azo 'dyestu s with diazotized anilin, substantiallyas described. 11; As new roducts lire'ids of substituted l s'ubs'tanc'escharhcterieed; by

9. As new products ureids-of substitutedv 10. As new products''ureidsofthssubsti- J tially as described and forming azo forniin saltswith metal? anilin. substandyestu s with diazotiz tially a's.described.

12."As new products ureids of substituted nminoniipht hol' substancescharacterized by containing in then molecule an aggregation of thegeneral group:

V mom in which n stands for the number-,ot hvilrogen atoms leftunsubstitflted in the naphthalene nucleus; forming salts with metals,

and forming uzo dyestuffs with (lia'zot-ize unilin, substantially asdescribed. l3. A new roclucts ureidsof substituted uminouuphthusu'listnnces characterized by containing in their molecule the vgeneralgroup: t i

i 40H I NHCOCaHr-NH t v. i 50,11 I V r formin salts with metals, andforming nzo 'dyestu s with dinzotized anili-nf'substun tin'lly hedescribed.

l-l. As new products ureids of substituted uminouaphthol substancescharacterized by containing in their molecule an aggregationof thegeneral grnupi' forming salts with ,itietals,-und forming am dyes-milswith diuzotizell uniliu, substanntiully' ns described;

As i u-.\\' p rmhu-ts urehlsof substituted :uuiunuuphthol substances.cl1u1'u.c tei'ized by containing in their forming salts with metals.and forming azo dyestuffs with diuzotized anil1n,;substan- '16. As new.roclucts ureids o f substituted in which A stands for the radicalof anaphthalene compound,- B stands for the molecule the general residue 01-an acid group, Y; stands for an nromatic radical, anrlZ represents ametaL,

flao

radical, formii-ig salts with metals. and 'forming uzo drestufl's withdiazotlzocl am loid; forming salts with metals, substonaminonaphtholsubstances characterized by t'ially nsjdescr-ibed. the following generalformula: 6

17. As new products ureids of substituted 1 on on CNlI--Il-C;-H.,NIL-CZ-NH-CH.,-lL-NH c in x M, H. XL,- Xuimd. forming nzodyestuffs with diuzotized auilin, substantially as described.

18. As new roducts nrcids of substituted in which It stands for theresidueof an acid group" n a number less than 7. X for substu tut ngroups, n :1 number less than live,

nml for substituting groups; 7 standing uuunouaphtho substancescharacterized by for a nwfnlloul; forming salts with metals thefollowing general formula: 15

011 1) I mus) --]t---l'7l;ll.,-N u co--uu-c.u. n-nn s 1o v H Cw H" hn!X4! l X0"! 6-1 in which R stands for u divalent group conforming uzoilycstull's with diazotized unilin, taining; an ucidyl radical, n anumber loss substantially as described. I than .seven, X forsubstituting groups, n' a 19. As new products urcids of substitutednumber less than 5, and X for substlt-uting amlnonaphthol substancescharacterized by groups; forming salts wlth metals, and the followinggeneral formula: 25

on -1 on H Nn-n c.n.,-Nu --cz r-1;-l--c.nn,-R--Nn Cw X m Xon H- (SJJIUMIin which. R stands fo: the residue of an acid 20. As new products ureidsof substituted- 7 roup, n a number loss than 7, n a number :umnonuphtholsubstances characterized by ess than five, Z for a metalloid; Aforsubthe following general formula: stituents, forming azo dycstufi'swith diazotized an'illn, substantially as described.

02m) A v 7 011(1 C um R-C1H,,NH-G9=-NHCH-1,RNH(8) c n. XH, XH, H.

solrgsd. 1K). in which R stands for a divalent group conforming nzodyestuffs with diazotized 'anitaining an acidyl radical, n a number lesshn, substantially as described. 40

21. As new rod'ucts ureids of substituted aminona-phtho i substancescharacterized by the following" general formula:

than 7, X for substituting groups, n enumber less than 5 and X forsubstitutm groups; forming salts with metals; an

in which R stands for an arid group, form 22'. Agni-u prorlurls rrrcidsof, substituted ing-salts' with metalsl'uhd forming azo dyc'umiuolmphtho'l [stances cl'ulrarterized by stuffs withdiazotized-nnilin, substuntiully jlu: following gem ll formula:

as described. I

in which R stands for a divalent acidyl' 23. As new products m oids ofsubstituted 5 5 umillonnphthol substzfiufcs chm-:wh-ri'nml by thefollowing general formula:

lin, suhs-tmuinlly as described.

divalent acidyl forming azo dyestuffs with diazotized ani- 6b in which Rstands for a. radical; forming salts with metals, and 1m, substantiallyas described.

'24. As new products ureids of substituterl aminona phthol substancescharacterized by in which n stands for a number less than 7, I As newproducts ureids of substituted and X for substituting groups; forminaniinonaphtlml substances cl'iaraeterized by 10 salts with metals, andforming azu dyestu s the following general formula-z with diazntizedanilin, substantially as described.

new i 1 one i uu a -ce-o.m-nn-co-n H nour-00 4w 3 C1 10 1 H. H 5

' X. Xsn H i l i I I i in which n stands for a number-less than 26. Asnew products urelds of substituted seven, and X for substituting groups;furmamincumphthul substances el'iaructerized by ingsa'lts with metals,and forming azo dye-' the following general formula:

stuffs with diazotized anilin, substantially as described.

on 0'11 i HH-CO-(-II-NH-CO--NII-CH4-CO-NII u i Cu.

11, n. i some, H ommin which n stands for a number less than 7 27. Asnew products ureirls of substituted forming salts with metals andforming azo nminonaphthnl substances characterized by dyestuffs withdlazotized anllm, substaw thefpllowing general formula: 25 tlall y asdescribed.

03m I 1 nuqa -co-ciurnu-eo-un-cini-co-nms u: i, 310

H H. l )$--l a ka in winch n stands for a number less than 28. As newFrwlucts ureids of substituted 30 seven, forming salts with metals, andformummrmaphtlm substances characterized by ing azn dyestu-fl's withdiazutized anilin, subthe following general fdrmula: stanhally asdescribed. a

\ NII-'C0--C H|-Iw |1--UO--NH---C Hi--C0-NH i H i H Lu:

I 1 (S0111): soul l'm-uiiug salts with nctals, and forming a-m 2! As nunprmluuts ureirls of substituted dyrstull's with iluimtizml :uul'iu,suhstan- :uuluuuaplithul subst'uurns characterized by tially asdescralzied. the following general formula:

(mm onus Nl*l(lJ--CO-Cdl --N1I UO-N1L--Ulh- U-Nl-l(l) U10 t 111 in sonunsome soium somw 'l'orming salts with metals, and firming am in testimonywhereof we have hereunto dyestull's with diaznti/ml unillu; suhstansetmu' hands in the priscnce of two sub- Linlly duscrit'ied. srriliiug'witnesses.

BERNHARD HEYMANN.

It] CHART) KOTHE. OSKAR DRESSEL. ANTON ()SSENBECK.

WItnuSSGS:

Cums Vamnnm; lihwnun Pawns.

